US5068365A - Hexahydrophthalic anilide derivatives - Google Patents

Hexahydrophthalic anilide derivatives Download PDF

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US5068365A
US5068365A US07/292,077 US29207788A US5068365A US 5068365 A US5068365 A US 5068365A US 29207788 A US29207788 A US 29207788A US 5068365 A US5068365 A US 5068365A
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compound
alkyl
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substituted
hexahydrophthalic
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US07/292,077
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Takumi Tokunaga
Hiroyuki Watanabe
Kenji Tsuzuki
Sinzo Someya
Seigo Koura
Mikio Ito
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Agro Kanesho Co Ltd
Tosoh Corp
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Agro Kanesho Co Ltd
Tosoh Corp
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Priority claimed from JP33645287A external-priority patent/JPH01175961A/en
Priority claimed from JP22225688A external-priority patent/JPH0272145A/en
Priority claimed from JP22546288A external-priority patent/JPH0273047A/en
Priority claimed from JP63234259A external-priority patent/JPH0283359A/en
Application filed by Agro Kanesho Co Ltd, Tosoh Corp filed Critical Agro Kanesho Co Ltd
Assigned to TOSOH CORPORATION, 4560, OOAZA TONDA, SIN-NAN-YOO-SHI, YAMAGUCHI 746, JAPAN, AGRO-KANESHO CO., LTD., 4-1, MARUNOUCHI 2-CHOME, CHIYODA-KU, TOKYO, 100 JAPAN reassignment TOSOH CORPORATION, 4560, OOAZA TONDA, SIN-NAN-YOO-SHI, YAMAGUCHI 746, JAPAN ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: ITO, MIKIO, SOMEYA, SINZO, TSUZUKI, KENJI, KOURA, SEIGO, TOKUNAGA, TAKUMI, WATANABE, HIROYUKI
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/06—1,2,4-Oxadiazoles; Hydrogenated 1,2,4-oxadiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/30—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the groups —CO—N< and, both being directly attached by their carbon atoms to the same carbon skeleton, e.g. H2N—NH—CO—C6H4—COOCH3; Thio-analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
    • A01N39/04—Aryloxy-acetic acids; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • A01N41/06—Sulfonic acid amides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/57—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C233/60—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/11—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound oxygen atoms bound to the same saturated acyclic carbon skeleton
    • C07C255/13—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound oxygen atoms bound to the same saturated acyclic carbon skeleton containing cyano groups and etherified hydroxy groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/22—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound oxygen atoms
    • C07C311/29—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound oxygen atoms having the sulfur atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/33—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring
    • C07C323/35—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group
    • C07C323/36—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group the sulfur atom of the sulfide group being further bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/42—Singly bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • This invention relates to novel hexahydropthalic acid anilide derivatives which have high herbicidal activity and selectivity.
  • some of the known hexahydrophthalic anilide derivatives do not have satisfactory herbicidal activity.
  • the other known hexahydrophthalic anilide derivatives do not have satisfactory selectivity. That is, when the herbicide comprising the derivative is applied to the crops and weeds, not only the weeds, but also the crops may be damaged. Thus, the safety of the herbicide is not good.
  • the object of the present invention is to provide novel hexahydrophthalic anilide derivatives which have a high herbicidal activity and selectivity.
  • Another object of the present invention is to provide herbicide compositions having a high herbicidal activity and selectivity.
  • the present inventors intensively studied to find that specific hexahydrophthalic anilide derivatives have a high herbicidal activity and selectivity to complete the present invention.
  • the present invention provides novel hexahydrophthalic anilide derivatives which are represented by one of the following formulae [I]-[III]: ##STR4## (wherein R 1 represents non-substituted or substituted phenyl, R 2 represents hydrogen or C 1 -C 5 alkyl, R 3 represents C 1 -C 5 alkyl or C 1 -C 5 alkenyl) ##STR5## (wherein R 4 and R 5 , the same or different, represent C 1 -C 6 alkyl, C 1 -C 6 alkenyl or C 1 -C 6 alkynyl, provided R 4 and R 5 are not C 1 -C 6 alkyl simultaneously) ##STR6## (wherein X 1 and X 2 , the same or different, represent halogen, Y represents oxygen or sulfur, R 6 represents C 1 -C 6 straight or cyclic alkyl which may be substituted with oxygen, R 7 represents hydrogen or methyl, R 8 represents cyano, C 1 -
  • novel hexahydrophthalic anilide derivatives with high herbicidal activity and selectivity was provided.
  • the hexahydrophthalic anilide derivatives of the present invention have a high herbicidal activity while they do not substantially damage the useful crops such as wheat, corn and soybean. Thus, they can be used safely for the inhibition of the growth of weeds in the field of such crops.
  • the present invention provides the hexahydrophthalic anilide derivative represented by the above-described formula [I].
  • R 1 is non-substituted or substituted phenyl
  • R 2 is hydrogen or C 1 -C 5 alkyl
  • R 3 is C 1 -C 5 alkyl or C 1 -C 5 alkenyl.
  • R 1 may include toluyl, xylyl, ethylphenyl, propylphenyl, butylphenyl and phenyl.
  • the most preferred R 1 is phenyl.
  • Preferred examples of R 2 may include hydrogen and straight or branched C 1 -C 5 alkyl such as methyl, ethyl and propyl.
  • R 3 may include straight or branched C 1 -C 5 alkyl such as methyl, ethyl and propyl, and C 3 or C 4 alkenyl such as allyl and butenyl. Among these, the most preferred are ethyl and allyl.
  • the present invention provides the novel hexahydrophthalic anilide derivative represented by the above-described formula [II].
  • R 4 and R 5 represent C 1 -C 6 alkyl, C 1 -C 6 alkenyl or C 1 -C 6 alkynyl. However, R 4 and R 5 are not C 1 -C 6 alkyl simultaneously.
  • R 4 and R 5 may include C 1 -C 6 , preferably C 1 -C 5 straight and branched alkyl such as methyl, ethyl, n-propyl and isopropyl; C 3 and C 4 alkenyl such as allyl, 2-methyl-2-propenyl and 2-butenyl; and C 3 and C 4 alkynyl such as propargyl, 1-methyl-2-propynyl and 2-butynyl.
  • the present invention provides the novel hexahydrophthalic anilide derivative represented by the above-described formula [III].
  • X 1 and X 2 represent halogen and they may be the same or different.
  • Preferred examples of X 1 and X 2 include fluorine and chlorine.
  • Y represents oxygen or sulfur.
  • R 6 represents straight or cyclic C 1 -C 6 alkyl which may be substituted with oxygen.
  • R 6 may include alkoxylalkyl such as methoxyethyl, ethoxyethyl, methoxypropyl and ethoxypropyl; and alkyl which is substituted with a heterocyclic ring containing oxygen such as 2-tetrahydrofuranylmethyl and 2-perhydropyranylmethyl. Among these, the most preferred are methoxyethyl and 2-tetrahydrofuranylmethyl.
  • R 7 represents hydrogen or methyl.
  • R 8 represents cyano, C 1 -C 3 alkyl, C 2 or C 3 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 alkynyl substituted with methoxy, CONHR 9 (R 9 is aromatic sulfonyl) or azole heterocyclic ring such as oxazolyl, imidazolyl, pyrazolyl, thiazolyl, oxadiazolyl and thiadiazolyl.
  • R 8 may include cyano; C 1 -C 3 alkyl such as methyl, ethyl, propyl and isopropyl; alkenyl such as vinyl, propenyl and butenyl; alkynyl such as ethynyl, propynyl and butynyl; alkynyl substituted with methoxy such as 3-methoxypropynyl, 4-mehtoxybutynyl and 5-methoxypentynyl; secondary amide of which nitrogen atom is substituted with sulfonyl such as methylphenylsulfonyl, chlorophenylsulfonyl and anisylsulfonyl; azole heterocyclic ring such as 5-(1,2,4-oxadiazolyl) of which 3-position is substituted with C 1 -C 3 alkyl such as methyl, ethyl and propyl.
  • hexahydrophthalic anilide derivative represented by the formula [I] may be prepared by reacting the aniline derivative represented by formula [IV] and the acid halide represented by formula [V] according to the following Equation 1: ##STR10##
  • X means halogen, preferably chlorine, bromine and iodine.
  • R 1 , R 2 and R 3 represent the same meaning as in formula [I].
  • the reaction may be conducted in an appropriate solvent under the presence of a base at a temperature ranging from 0° C.-150° C., preferably 20° C.-100° C. for several minutes to 48 hours.
  • Preferred examples of the solvents which may be employed in the reaction may include ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene and xylene; ethers such as ethyl ether, tetrahydrofuran and dioxane; halogenated hydrocarbons such as chlorobenzene, chloroform, tetrachloromethane and dichloroethane; tertiary amines such as triethylamine, pyridine and dimethylaniline; and polar solvents such as acetonitrile, dimethylformamide, dimethylsulfoxide and hexamethylphosphoramide.
  • ketones such as acetone and methyl ethyl ketone
  • aromatic hydrocarbons such as benzene and xylene
  • ethers such as ethyl ether, tetrahydrofuran and dioxane
  • halogenated hydrocarbons such as chlor
  • Preferred examples of the bases which may be employed in the reaction may include amines such as triethylamine, pyridine, 1,3-diazabicyclo[5,4,0]undec-7-ene and dimethylaniline; alkali metal hydroxide such as sodium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; alkaline metal salts of carbonic acid such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate; and metal hydrides such as sodium hydride.
  • amines such as triethylamine, pyridine, 1,3-diazabicyclo[5,4,0]undec-7-ene and dimethylaniline
  • alkali metal hydroxide such as sodium hydroxide
  • alkaline earth metal hydroxides such as calcium hydroxide
  • alkaline metal salts of carbonic acid such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate
  • metal hydrides such as sodium hydride.
  • the hexahydrophthalic anilide derivative represented by formula [II] may be prepared by reacting the aniline derivative represented by formula [VI] and the acid halide represented by formula [VII] according to the following Equation 2: ##STR11##
  • Equation 2 X represents the same meaning as in Equation 1
  • R 4 and R 5 represent the same meaning as in formula [II].
  • the reaction may be conducted in the same conditions as in Equation 1.
  • the solvents and bases which are preferred in Equation 1 are also preferred in this reaction.
  • hexahydrophthalic anilide derivative represented by formula [III] may be prepared by reacting the aniline derivative represented by formula [IX] and the acid halide represented by formula [VIII] according to the following Equation 3: ##STR12##
  • Equation 3 X represents the same meaning as in Equation 1, X 1 , X 2 , R 6 , R 7 and R 8 represent the same meaning as in formula [III].
  • the reaction may be conducted in the same conditions as in Equation 1.
  • the solvents and bases which are preferred in Equation 1 are also preferred in these reactions.
  • the present invention further provides a herbicide composition comprising the hexahydrophthalic anilide derivative of the present invention as effective ingredient in an agriculturally acceptable carrier.
  • the herbicide composition of the present invention is effective for inhibiting the growth of various weeds growing in paddy field including the weeds belonging to the Gamineae such as barnyardgrass; broadleaved weeds such as Falsepinpernel, spindle-flowered rotala, water starwart and monochoria; and those belonging to the family cyperaceae such as small flower umbrellaplant, slender spikerush and water nutgrass.
  • the hexahydrophthalic anilide derivative of the present invention is particularly effective for inhibiting the growth of weeds growing in fields, such as mustard, virginia pepperweed, catchweed badstraw, Kinutaso (Galium kinuta), chick weed, Common lambsquaters, nottle (Utrica Thunbergiana), Common groundsel, Slender amaranth, Cocklebur, Pale smartweed, Velvetleaf and barynard grass.
  • the herbicide composition of the present invention does not substantially damage the crops belonging to Family Graminae such as corn, rice and wheat, so that it is highly safe.
  • liquid carrier or solid carrier may be employed.
  • liquid carrier or diluent may include water, hydrocarbons, ethers, alkoxy alcohols, ketones, esters, amides and sulfoxides.
  • Preferred examples of the solid carriers or extender may include powder and granules of inorganic materials such as slaked lime, gypsum, calcium carbonate, silica, pearlite, pumice, diatomaceous earth, alumina, zeolite and clay minerals (e.g., talc, vermiculite and kaolinite); powder and granules of plant products such as starch, cereals and glucose; and powder and granules of synthetic products such as phenol resins, carbon resins and vinyl chloride resins.
  • the concentration of the active ingredient in the composition is not critical and may usually be 0.1% by weight to 90% by weight, preferably 1% by weight to 80% by weight.
  • the herbicide composition of the present invention may contain a surfactant.
  • the surfactants are well-known and widely used in the art.
  • Preferred examples of the surfactants include anion surfactants such as alkylsulfate esters, arylsulfonic acids, salts of succinic acid and polyethyleneglycolalkylaryl ethers and ester salts of sulfuric acid; cation surfactants such as alkylamines and polyoxyethylenealkylamines; non-ionic surfactants such as polyoxyethyleneglycol ethers and polyol esters; and ampholytic surfactants.
  • the herbicide composition of the present invention may contain other additives which are often employed in herbicide compositions.
  • the examples of such additives may include stabilizers, dispersion stabilizers, fixing agents, effect prolongers and synergists.
  • the herbicide composition of the present invention may also contain other herbicides, bacteriocides, fungicides and the like.
  • the herbicide composition may be formulated to an emulsifiable concentrate, wettable powder, aqueous solution, oily solution, granule or powder.
  • the methods of formulating herbicide composition are well-known in the art.
  • This formulation may be prepared by uniformly mixing the components.
  • This composition may be prepared by mixing and pulverizing the components.
  • the amount of the compound of the present invention to be applied to the field varies depending on the formulation of the composition, method of application, species and stage of growth of the weeds. Typically, the amount to be applied may be 0.01 kg to 10 kg, preferably 0.05 kg to 5 kg per hectare in terms of the weight of the active ingredient of the present invention.
  • the herbicide composition of the present invention may directly be applied to the leaves or stems of weeds or to the field before the germination of the weeds
  • the herbicide composition may be applied as it is or may be diluted with water before use.
  • Example 3 Substantially the same operation as in Example 1 was repeated except that 1,2,3,4,5,6-hexahydrophthalic acid monoallyl ester was used as the hexahydrophthalic acid monlalkyl ester and 4-chloro-2-fluoro5-(1-phenylethyloxy)aniline was used as the anilide derivative to obtain the Compound No. 3.
  • Paddy field soil was packed in a plastic pot with 60 cm diameter. After pudding, the seeds of weeds shown in Table 4 below were sown and one seedling of rice (variety: Yamahoshi) with 2 leaves were transplanted. The water level was kept at about 3 cm above the soil.
  • the herbicide compositions formulated according to the above-described Formulation 2 which contained the Compound No. 1, 2 or 3 was diluted with water and was uniformly applied to the water surface in the amount shown in Table 4. Further, for comparison, N-(4-chloro-2-fluoro-5-isopropoxyphenyl)2-ethoxycarbonyl cyclohexyl carboxylic amide (Comparative Compound A) disclosed in Japanese Patent Disclosure (Kokai) No. 33154/86 was also tested. After 20 days from the application of the herbicide, the growing conditions of the weeds and the rice were observed. The growth inhibition was rated in 6 ranks as follows: follows:
  • the extract was washed with saturated aqueous sodium hydrogen carbonate and dried over magnesium sulfate.
  • Example 6 Substantially the same operation as in Example 6 was repeated except that 2-chlorocarbonyl-1-cyclohexane carboxylic acid allyl ester was used as the acid halide, and 4-chloro-2-fluoro-5-isopropoxyaniline was used as the aniline derivative to obtain the Compound No. 6.
  • Example 6 Substantially the same operation as in Example 6 was repeated except that 2-chlorocarbonyl-1-cyclohexane carboxylic acid allyl ester was used as the acid halide and 4-chloro-2-fluoro-5-propargyloxyaniline was used as the aniline derivative to obtain the Compound No. 9.
  • Example 6 Substantially the same operation as in Example 6 was repeated except that 2-chlorocarbonyl-1-cyclohexane carboxylic acid propargyl ester was used as the acid halide and 4-chloro-2-fluoro-5-propargyloxyaniline was used as the aniline derivative to obtain the Compound No. 11.
  • Example 6 Substantially the same operation as in Example 6 was repeated except that 2-chlorocarbonyl-1-cyclohexane carboxylic acid allyl ester was used as the acid halide and 4-chloro-2-fluoro-5-(1-methyl-propynyloxy)aniline was used as the aniline derivative to obtain the Compound No. 12.
  • Example 6 Substantially the same operation as in Example 6 was repeated except that 2-chlorocarbonyl-1-cyclohexane carboxylic acid propargyl ester was used as the acid halide and 4-chloro-2-fluoro-5-(1-methyl-propenyloxy)aniline was used as the aniline derivative to obtain the Compound No. 13.
  • Example 5 The same procedure as in Example 5 was repeated except that the compounds tested were Compound Nos. 4-13. Further, for comparison, the Comparative Compound A described in Example 4 was also tested. The results are shown in Table 6 below.
  • Example 7 The same procedure as in Example 4 was repeated except that the compounds tested were Compound Nos. 4-13.
  • the Comparative Compound A described in Example 4 was also tested. The results are shown in Table 7 below.
  • the extract was washed with saturated aqueous sodium hydrogen carbonate solution and was dried over anhydrous magnesium sulfate.
  • Example 21 Substantially the same procedure as in Example 21 was repeated except that 2-chlorocarbonyl-1-cyclohexane carboxylic acid 2-tetrahydrofuranylmethyl ester was used as the acid halide to obtain the Compound No. 22.
  • Example 18 Substantially the same procedure as in Example 18 was repeated except that 4-chloro-2-fluoro-5-[1-(3-methyl-1,2,4-oxadiazol-5-yl) ethoxy)aniline was used as the aniline derivative to obtain the Compound No. 24.
  • Example 4 The same procedure as in Example 4 was repeated except that the compounds tested were Compound Nos. 14-25. For comparison, the Comparative Compound A described in Example 4 was also tested. The results are shown in Table 8 below.
  • Example 9 The same procedure as in Example 5 was repeated except that the compounds tested were Compound Nos. 14-25. Further, for comparison, the Comparative Compound A described in Example 4 was also tested. The results are shown in Table 9 below.

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Abstract

Disclosed is novel hexahydrophthalic anilide derivatives and herbicide compositions comprising the derivatives. The hexahydrophthalic anilide derivatives of this invention are represented by the formula [I], [II] or [III]. ##STR1## (wherein R1 represents non-substituted or substituted phenyl, R2 represents hydrogen or C1 -C4 alkyl, R3 represents C1 -C4 alkyl or C1 -C4 alkenyl) ##STR2## (wherein R4 and R5, the same or different, represent C1 -C4 alkyl, C1 -C4 alkenyl or C1 -C4 alkynyl, provided R4 and R5 are not C1 -C4 alkyl simultaneously) ##STR3## (wherein X1 and X2, the same or different, represent halogen, Y represents oxygen or sulfur, R6 represents C1 -C6 straight or cyclic alkyl which may be substituted with oxygen, R7 represents hydrogen or methyl, R8 represents cyano, C1 -C3 alkyl, C2 or C3 alkenyl, C2 -C4 alkynyl, C3 -C6 alkynyl which is substituted with methoxy, CONHR9 (wherein R9 represents aromatic sulfonyl) or azole heterocyclic ring)

Description

BACKGROUND OF THE INVENTION
I. Field of the Invention
This invention relates to novel hexahydropthalic acid anilide derivatives which have high herbicidal activity and selectivity.
II. Description of the Related Art
The herbicidal activity of hexahydrophthalic anilide derivatives is well-known in the art. For example, Japanese Patent Disclosure (Kokai) No. 33154/86 discloses N-(4-chloro-2-fluoro-5-isopropoxyphenyl)-2-ethoxycarbonylcyclohexylcarboxylic amide.
However, some of the known hexahydrophthalic anilide derivatives do not have satisfactory herbicidal activity. The other known hexahydrophthalic anilide derivatives do not have satisfactory selectivity. That is, when the herbicide comprising the derivative is applied to the crops and weeds, not only the weeds, but also the crops may be damaged. Thus, the safety of the herbicide is not good.
SUMMARY OF THE INVENTION
Accordingly, the object of the present invention is to provide novel hexahydrophthalic anilide derivatives which have a high herbicidal activity and selectivity.
Another object of the present invention is to provide herbicide compositions having a high herbicidal activity and selectivity.
The present inventors intensively studied to find that specific hexahydrophthalic anilide derivatives have a high herbicidal activity and selectivity to complete the present invention.
That is, the present invention provides novel hexahydrophthalic anilide derivatives which are represented by one of the following formulae [I]-[III]: ##STR4## (wherein R1 represents non-substituted or substituted phenyl, R2 represents hydrogen or C1 -C5 alkyl, R3 represents C1 -C5 alkyl or C1 -C5 alkenyl) ##STR5## (wherein R4 and R5, the same or different, represent C1 -C6 alkyl, C1 -C6 alkenyl or C1 -C6 alkynyl, provided R4 and R5 are not C1 -C6 alkyl simultaneously) ##STR6## (wherein X1 and X2, the same or different, represent halogen, Y represents oxygen or sulfur, R6 represents C1 -C6 straight or cyclic alkyl which may be substituted with oxygen, R7 represents hydrogen or methyl, R8 represents cyano, C1 -C3 alkyl, C2 or C3 alkenyl, C2 -C4 alkynyl, C3 -C6 alkynyl which is substituted with methoxy, CONHR9 (wherein R9 represents aromatic sulfonyl) or azole heterocyclic ring)
By the present invention, novel hexahydrophthalic anilide derivatives with high herbicidal activity and selectivity was provided. As will be clearly demonstrated in the Examples later described, the hexahydrophthalic anilide derivatives of the present invention have a high herbicidal activity while they do not substantially damage the useful crops such as wheat, corn and soybean. Thus, they can be used safely for the inhibition of the growth of weeds in the field of such crops.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In one aspect, the present invention provides the hexahydrophthalic anilide derivative represented by the above-described formula [I]. In formula [I], R1 is non-substituted or substituted phenyl, R2 is hydrogen or C1 -C5 alkyl and R3 is C1 -C5 alkyl or C1 -C5 alkenyl. Preferred examples of R1 may include toluyl, xylyl, ethylphenyl, propylphenyl, butylphenyl and phenyl. The most preferred R1 is phenyl. Preferred examples of R2 may include hydrogen and straight or branched C1 -C5 alkyl such as methyl, ethyl and propyl. Among these, the most preferred are hydrogen and methyl. Preferred examples of R3 may include straight or branched C1 -C5 alkyl such as methyl, ethyl and propyl, and C3 or C4 alkenyl such as allyl and butenyl. Among these, the most preferred are ethyl and allyl.
Preferred and non-limiting specific examples of the hexahydrophthalic anilide derivatives represented by the formula [I] are summarized in Table 1 below.
              TABLE 1                                                     
______________________________________                                    
Compound No. R.sup.1      R.sup.2                                         
                                 R.sup.3                                  
______________________________________                                    
1            phenyl       H      C.sub.2 H.sub.5                          
2            phenyl       CH.sub.3                                        
                                 C.sub.2 H.sub.5                          
3            phenyl       CH.sub.3                                        
                                 allyl                                    
______________________________________
In another aspect, the present invention provides the novel hexahydrophthalic anilide derivative represented by the above-described formula [II]. In the formula [II], R4 and R5, the same or different, represent C1 -C6 alkyl, C1 -C6 alkenyl or C1 -C6 alkynyl. However, R4 and R5 are not C1 -C6 alkyl simultaneously. Preferred examples of R4 and R5 may include C1 -C6, preferably C1 -C5 straight and branched alkyl such as methyl, ethyl, n-propyl and isopropyl; C3 and C4 alkenyl such as allyl, 2-methyl-2-propenyl and 2-butenyl; and C3 and C4 alkynyl such as propargyl, 1-methyl-2-propynyl and 2-butynyl.
Preferred and non-limiting specific examples of the hexahydrophthalic anilide derivative of formula [II] are listed in Table 2 below.
              TABLE 2                                                     
______________________________________                                    
Compound No. R.sup.4     R.sup.5                                          
______________________________________                                    
4            C.sub.2 H.sub.5                                              
                         CH.sub.2 CH=CH.sub.2                             
5            C.sub.2 H.sub.5                                              
                         CH.sub.2 C≡CH                              
6            CH.sub.2 CH=CH.sub.2                                         
                         CH(CH.sub.3).sub.2                               
7            CH.sub.2 C≡CH                                          
                         CH(CH.sub.3).sub.2                               
8            CH.sub.2 CH=CH.sub.2                                         
                         CH.sub.2 CH=CH.sub.2                             
9            CH.sub.2 CH=CH.sub.2                                         
                         CH.sub.2 C≡CH                              
10           CH.sub.2 C≡CH                                          
                         CH.sub.2 CH=CH.sub.2                             
11           CH.sub.2 C≡CH                                          
                         CH.sub.2 C≡CH                              
12           CH.sub.2 CH=CH.sub.2                                         
                         CH(CH.sub.3)C≡CH                           
13           CH.sub.2 C≡CH                                          
                         CH(CH.sub.3)CH=CH.sub.2                          
______________________________________
In still another aspect, the present invention provides the novel hexahydrophthalic anilide derivative represented by the above-described formula [III]. In formula [III], X1 and X2 represent halogen and they may be the same or different. Preferred examples of X1 and X2 include fluorine and chlorine. Y represents oxygen or sulfur. R6 represents straight or cyclic C1 -C6 alkyl which may be substituted with oxygen. Preferred examples of R6 may include alkoxylalkyl such as methoxyethyl, ethoxyethyl, methoxypropyl and ethoxypropyl; and alkyl which is substituted with a heterocyclic ring containing oxygen such as 2-tetrahydrofuranylmethyl and 2-perhydropyranylmethyl. Among these, the most preferred are methoxyethyl and 2-tetrahydrofuranylmethyl. R7 represents hydrogen or methyl. R8 represents cyano, C1 -C3 alkyl, C2 or C3 alkenyl, C2 -C4 alkynyl, C3 -C6 alkynyl substituted with methoxy, CONHR9 (R9 is aromatic sulfonyl) or azole heterocyclic ring such as oxazolyl, imidazolyl, pyrazolyl, thiazolyl, oxadiazolyl and thiadiazolyl. Preferred examples of R8 may include cyano; C1 -C3 alkyl such as methyl, ethyl, propyl and isopropyl; alkenyl such as vinyl, propenyl and butenyl; alkynyl such as ethynyl, propynyl and butynyl; alkynyl substituted with methoxy such as 3-methoxypropynyl, 4-mehtoxybutynyl and 5-methoxypentynyl; secondary amide of which nitrogen atom is substituted with sulfonyl such as methylphenylsulfonyl, chlorophenylsulfonyl and anisylsulfonyl; azole heterocyclic ring such as 5-(1,2,4-oxadiazolyl) of which 3-position is substituted with C1 -C3 alkyl such as methyl, ethyl and propyl.
Preferred and non-limiting specific examples of the hexahydrophthalic anilide derivative represented by the formula [III] are listed in Table 3 below.
                                  TABLE 3                                 
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Compound No.                                                              
        X.sup.1                                                           
          X.sup.2                                                         
            Y R.sup.6  R.sup.7                                            
                          R.sup.8                                         
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14      F Cl                                                              
            O CH.sub.2 CH.sub.2 OMe                                       
                       Me Me                                              
15      F Cl                                                              
            S CH.sub.2 CH.sub.2 OMe                                       
                       H  CHCH.sub.2                                      
16      F Cl                                                              
            O CH.sub.2 CH.sub.2 OMe                                       
                       H  CCH                                             
17      F Cl                                                              
            O CH.sub.2 CH.sub.2 OMe                                       
                       Me CCH                                             
18      F Cl                                                              
            O CH.sub.2 CH.sub.2 OMe                                       
                       Me CH.sub.2 CCH                                    
19      F Cl                                                              
            O CH.sub.2 CH.sub.2 OMe                                       
                       H  CCCH.sub.2 OMe                                  
20      F Cl                                                              
            S CH.sub.2 CH.sub.2 OMe                                       
                       H  CCH                                             
21      Cl                                                                
          Cl                                                              
            O CH.sub.2 CH.sub.2 OMe                                       
                       Me CCH                                             
22      F Cl                                                              
            O                                                             
               ##STR7##                                                   
                       Me CCH                                             
23      F Cl                                                              
            O CH.sub.2 CH.sub.2 OMe                                       
                       Me CN                                              
24      F Cl                                                              
            O CH.sub.2 CH.sub.2 OMe                                       
                       Me                                                 
                           ##STR8##                                       
25      F Cl                                                              
            O CH.sub.2 CH.sub.2 OMe                                       
                       Me                                                 
                           ##STR9##                                       
__________________________________________________________________________
 Me: CH.sub.3
The hexahydrophthalic anilide derivative represented by the formula [I] may be prepared by reacting the aniline derivative represented by formula [IV] and the acid halide represented by formula [V] according to the following Equation 1: ##STR10##
In the above Equation 1, X means halogen, preferably chlorine, bromine and iodine. R1, R2 and R3 represent the same meaning as in formula [I].
The reaction may be conducted in an appropriate solvent under the presence of a base at a temperature ranging from 0° C.-150° C., preferably 20° C.-100° C. for several minutes to 48 hours.
Preferred examples of the solvents which may be employed in the reaction may include ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene and xylene; ethers such as ethyl ether, tetrahydrofuran and dioxane; halogenated hydrocarbons such as chlorobenzene, chloroform, tetrachloromethane and dichloroethane; tertiary amines such as triethylamine, pyridine and dimethylaniline; and polar solvents such as acetonitrile, dimethylformamide, dimethylsulfoxide and hexamethylphosphoramide.
Preferred examples of the bases which may be employed in the reaction may include amines such as triethylamine, pyridine, 1,3-diazabicyclo[5,4,0]undec-7-ene and dimethylaniline; alkali metal hydroxide such as sodium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; alkaline metal salts of carbonic acid such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate; and metal hydrides such as sodium hydride.
Typically, 1-5 equivalents of the aniline derivative [IV] and 1-10 equivalents of the base are reacted with 1 equivalent of the acid halide [V].
The hexahydrophthalic anilide derivative represented by formula [II] may be prepared by reacting the aniline derivative represented by formula [VI] and the acid halide represented by formula [VII] according to the following Equation 2: ##STR11##
In the above Equation 2, X represents the same meaning as in Equation 1, R4 and R5 represent the same meaning as in formula [II].
The reaction may be conducted in the same conditions as in Equation 1. The solvents and bases which are preferred in Equation 1 are also preferred in this reaction.
Typically, 1-5 equivalents of the aniline derivative [VII] and 1-10 equivalents of the base are reacted with 1 equivalent of the acid halide [VI].
The hexahydrophthalic anilide derivative represented by formula [III] may be prepared by reacting the aniline derivative represented by formula [IX] and the acid halide represented by formula [VIII] according to the following Equation 3: ##STR12##
In the above Equation 3, X represents the same meaning as in Equation 1, X1, X2, R6, R7 and R8 represent the same meaning as in formula [III].
The reaction may be conducted in the same conditions as in Equation 1. The solvents and bases which are preferred in Equation 1 are also preferred in these reactions.
Typically, 1-5 equivalents of the aniline derivative [IX] and 1-10 equivalents of the base are reacted with 1 equivalent of the acid halide [VIII].
The present invention further provides a herbicide composition comprising the hexahydrophthalic anilide derivative of the present invention as effective ingredient in an agriculturally acceptable carrier. The herbicide composition of the present invention is effective for inhibiting the growth of various weeds growing in paddy field including the weeds belonging to the Gamineae such as barnyardgrass; broadleaved weeds such as Falsepinpernel, spindle-flowered rotala, water starwart and monochoria; and those belonging to the family cyperaceae such as small flower umbrellaplant, slender spikerush and water nutgrass. Further, the hexahydrophthalic anilide derivative of the present invention is particularly effective for inhibiting the growth of weeds growing in fields, such as mustard, virginia pepperweed, catchweed badstraw, Kinutaso (Galium kinuta), chick weed, Common lambsquaters, nottle (Utrica Thunbergiana), Common groundsel, Slender amaranth, Cocklebur, Pale smartweed, Velvetleaf and barynard grass. The herbicide composition of the present invention does not substantially damage the crops belonging to Family Graminae such as corn, rice and wheat, so that it is highly safe.
The agriculturally acceptable carriers per se which may be employed in the present invention are well-known in the art, and either liquid carrier or solid carrier may be employed. Preferred examples of the liquid carrier or diluent may include water, hydrocarbons, ethers, alkoxy alcohols, ketones, esters, amides and sulfoxides. Preferred examples of the solid carriers or extender may include powder and granules of inorganic materials such as slaked lime, gypsum, calcium carbonate, silica, pearlite, pumice, diatomaceous earth, alumina, zeolite and clay minerals (e.g., talc, vermiculite and kaolinite); powder and granules of plant products such as starch, cereals and glucose; and powder and granules of synthetic products such as phenol resins, carbon resins and vinyl chloride resins. The concentration of the active ingredient in the composition is not critical and may usually be 0.1% by weight to 90% by weight, preferably 1% by weight to 80% by weight.
If necessary, the herbicide composition of the present invention may contain a surfactant. The surfactants are well-known and widely used in the art. Preferred examples of the surfactants include anion surfactants such as alkylsulfate esters, arylsulfonic acids, salts of succinic acid and polyethyleneglycolalkylaryl ethers and ester salts of sulfuric acid; cation surfactants such as alkylamines and polyoxyethylenealkylamines; non-ionic surfactants such as polyoxyethyleneglycol ethers and polyol esters; and ampholytic surfactants. If desired, the herbicide composition of the present invention may contain other additives which are often employed in herbicide compositions. The examples of such additives may include stabilizers, dispersion stabilizers, fixing agents, effect prolongers and synergists. The herbicide composition of the present invention may also contain other herbicides, bacteriocides, fungicides and the like.
The herbicide composition may be formulated to an emulsifiable concentrate, wettable powder, aqueous solution, oily solution, granule or powder. The methods of formulating herbicide composition are well-known in the art.
Specific non-limiting examples of the preferred compositions of the present invention will now be described. In the following examples, all parts are based on weight.
FORMULATION 1 Emulsifiable Concentrate 
______________________________________                                    
Compound of the present invetnion:                                        
                       20 parts                                           
xylene:                60 parts                                           
Solpol (a surfactant commercially                                         
                       20 parts                                           
available from Toho Kogaku Kogyo)                                         
______________________________________
This formulation may be prepared by uniformly mixing the components.
FORMULATION 2 Wettable Powder 
______________________________________                                    
Compound of the present invetnion                                         
                         10 parts                                         
Zeaklite                 87 parts                                         
Neoplex Powder (commercially                                              
                          1.5 parts                                       
available rom Kao corporation)                                            
Solpol (a surfactant commercially                                         
                          1.5 parts                                       
available from Toho Kogaku Kogyo)                                         
______________________________________
This composition may be prepared by mixing and pulverizing the components.
The amount of the compound of the present invention to be applied to the field varies depending on the formulation of the composition, method of application, species and stage of growth of the weeds. Typically, the amount to be applied may be 0.01 kg to 10 kg, preferably 0.05 kg to 5 kg per hectare in terms of the weight of the active ingredient of the present invention.
The herbicide composition of the present invention may directly be applied to the leaves or stems of weeds or to the field before the germination of the weeds The herbicide composition may be applied as it is or may be diluted with water before use.
The invention will now be described by way of the examples thereof. It should be understood that the examples are presented for the illustration purpose only and should not be interpreted any restrictive way.
EXAMPLE 1 Preparation of N-(5-benzyloxy-4-chloro-2-fluorophenyl)2-ethoxycarbonyl cyclohexyl carboxylic amide (Compound No. 1 (Table 1))
In 20 ml of methylene chloride, 400 mg of 1,2,3,4,5,6-hexahydrophthalic acid monoethylester was dissolved. To this solution, 0.16 ml of pyridine and 0.16 ml of thionyl chloride were added and the mixture was stirred at room temperature. One hour later, 0.45 g of 5-benzyloxy-4-chloro-2-fluoroaniline and 10 ml of triethylamine were added and the resulting mixture was stirred at room temperature for 2.5 hours. After completion of the reaction, 10% hydrochloric acid was added to the reaction mixture to make the mixture acidic and the resulting mixture was extracted twice with methylene chloride. The extract was washed with saturated aqueous sodium hydrogen carbonate solution and was dried over anhydrous magnesium sulfate. The solvent was then evaporated and the residue was purified by column chromatography (silica gel, hexane/ethyl acetate =3/1 (v/v)) to obtain 0.35 g of solid.
m.p.: 78° C.-80° C.
______________________________________                                    
Element Analysis                                                          
         C           H      N                                             
______________________________________                                    
Found (%)  63.89         5.75   2.85                                      
Calcd. (%) 63.66         5.80   3.22                                      
______________________________________
IR (KBr, cm-1): 3320, 1725, 1690
PMR (CDCl3, δ ppm) 1.10-2.40 (m, 11H), 2.56-3.20 (m, 2H), 4.10 (q, J =7 Hz, 2H), 5.10 (s, 2H), 7.06 (d, J =10 Hz, 1H), 7.15-7.55 (m, 5H), 7.70 (brs, 1H), 8.16 (d, J =7 Hz, 1H)
EXAMPLE 2 Preparation of Compound No. 2
Substantially the same operation as in Example 1 was repeated except that 4-chloro-2-fluoro-5-(1-phenylethyloxy)aniline was used as the aniline derivative to obtain the Compound No. 2.
m.p.: 108° C.-110° C.
______________________________________                                    
Element Analysis                                                          
         C           H      N                                             
______________________________________                                    
Found (%)  64.15         6.03   3.31                                      
Calcd. (%) 64.35         6.07   3.12                                      
______________________________________
IR (KBr, cm-1): 3320, 1725, 1690
PMR (CDCl3, δ ppm) 0.90-2.45 (m, 14H), 2.50-3.10 (m, 2H), 4.09 (q, J =7 Hz, 2H), 5.39 (q, J =6 Hz, 1H), 7.00 (d, J =10 Hz, 1H), 7.10-7.50 (m, 5H), 7.68 (brs, 1H), 8.03 (d, J =7 Hz, 1H)
EXAMPLE 3 Preparation of Compound No. 3
Substantially the same operation as in Example 1 was repeated except that 1,2,3,4,5,6-hexahydrophthalic acid monoallyl ester was used as the hexahydrophthalic acid monlalkyl ester and 4-chloro-2-fluoro5-(1-phenylethyloxy)aniline was used as the anilide derivative to obtain the Compound No. 3.
m.p.: 54° C.-56° C.
______________________________________                                    
Element Analysis                                                          
         C           H      N                                             
______________________________________                                    
Found (%)  65.21         5.87   3.14                                      
Calcd. (%) 65.28         5.91   3.04                                      
______________________________________
IR (KBr, cm-1) 3320, 1725, 1690
PMR (CDCl3, δ ppm) 1.00-2.50 (m, 11H), 2.50-3.15 (m, 2H), 4.52 (d, J =5 Hz, 2H), 4.90-6.22 (m, 4HO, 7.00 (d, J =10 Hz, 1H), 7.05-7.53 (m, 5H), 7.58 (brs, 1H), 8.03 (d, J =7 Hz, 1H)
EXAMPLE 4 Test for Evaluation of Effectiveness in Growth Inhibition by Soil Treatment
Paddy field soil was packed in a plastic pot with 60 cm diameter. After pudding, the seeds of weeds shown in Table 4 below were sown and one seedling of rice (variety: Yamahoshi) with 2 leaves were transplanted. The water level was kept at about 3 cm above the soil. The herbicide compositions formulated according to the above-described Formulation 2 which contained the Compound No. 1, 2 or 3 was diluted with water and was uniformly applied to the water surface in the amount shown in Table 4. Further, for comparison, N-(4-chloro-2-fluoro-5-isopropoxyphenyl)2-ethoxycarbonyl cyclohexyl carboxylic amide (Comparative Compound A) disclosed in Japanese Patent Disclosure (Kokai) No. 33154/86 was also tested. After 20 days from the application of the herbicide, the growing conditions of the weeds and the rice were observed. The growth inhibition was rated in 6 ranks as follows: follows:
Rank 0: percent growth inhibition of 0%-9%
Rank 1: percent growth inhibition of 10%-29%
Rank 2: percent growth inhibition of 30%-49%
Rank 3: percent growth inhibition of 50%-69%
Rank 4: percent growth inhibition of 70%-89%
Rank 5: percent growth inhibition of 90%-100%
The results are shown in Table 4.
                                  TABLE 4                                 
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                                    Annual                                
Compound                                                                  
       Rate     Barnyard-                                                 
                      Small flower  broadleaved                           
No.    (a.i. g/10a)                                                       
             Rice                                                         
                grass umbrellaplant                                       
                             Monochoria                                   
                                    weeds                                 
__________________________________________________________________________
1      250   0  5     5      5      5                                     
       125   0  5     5      5      5                                     
        60   0  5     4      4      5                                     
2      250   0  5     5      5      5                                     
       125   0  5     5      5      5                                     
        60   0  5     5      5      5                                     
3      250   0  5     5      5      5                                     
       125   0  5     5      5      5                                     
        60   0  5     5      5      5                                     
Compara-                                                                  
       250   4  5     5      5      5                                     
tive   125   4  5     5      5      5                                     
Compound A                                                                
        60   3  5     5      5      5                                     
__________________________________________________________________________
EXAMPLE 5 Test for Evaluation of Effectiveness in Growth Inhibition by Foliage Treatment
Field soil was packed in a plastic vat sizing 22 cm ×16 cm and seeds of wheat (Triticum aestivum), corn (Zea mays) and soybean (Glycine max) were sown. The field soil was covered with soil of about 1 cm thickness which contains seeds of weeds, i.e., Slender amaranth, Velvetleaf and Cocklebur. When the barnyardgrass grew to have 2-2.5 leaves, the Compound No. 3 of the present invention was applied in the amount shown in Table 5 below. Further, for comparison, the comparative compound A described in Example 4 was also applied. After 14 days from the application of the herbicide, the conditions of the growth of the weeds and the crops were observed. The results are shown in Table 5. The herbicidal effectiveness was rated in 6 ranks as in Example 4.
                                  TABLE 5                                 
__________________________________________________________________________
Compound                                                                  
       Rate              Slender                                          
No.    (a.i. g/10a)                                                       
             Soybean                                                      
                  Wheat                                                   
                      Corn                                                
                         amaranth                                         
                              Velvetleaf                                  
                                    Cocklebur                             
__________________________________________________________________________
3      250   0    0   0  5    5     4                                     
       125   0    0   0  5    5     4                                     
        60   0    0   0  5    5     3                                     
Compara-                                                                  
       250   4    0   0  5    5     5                                     
tive   125   4    0   0  5    5     5                                     
Compound D                                                                
        60   3    0   0  5    5     5                                     
__________________________________________________________________________
EXAMPLE 6 Preparation of N-(5-allyloxy-4-chloro-2-fluorophenyl)-2-ethoxycarbonyl cyclohexyl carboxylic amide (Compound No. 4)
In 20 ml of methylene chloride, 1.20 g of 1,2,3,4,5,6-hexahydrophthalic acid monoethyl ester was dissolved. To this solution 0.47 g of pyridine and 0.71 g of thionyl chloride were added and the resulting mixture was stirred at room temperature. Two hour later, 1 20 g of 5-allyloxy-4-chloro-2-fluoroaniline and 0.61 g of triethylamine were added and the resulting mixture was stirred at room temperature for 5 hours. After completion of the reaction, 10% hydrochloric acid was added to the reaction mixture to make the same acidic and was extracted twice with methylene chloride. The extract was washed with saturated aqueous sodium hydrogen carbonate and dried over magnesium sulfate. The solvent was evaporated under reduced pressure and the residue was purified by column chromatography (silica gel, hexane/ethyl acetate =5/1 (v/v)) to obtain 1.5 g of light brown crystal.
m.p.: 52° C.-53° C.
1 H-NMR (CDCl3, δ ppm) 1.17 (3H, t), 1.10-2.50 (8H, m), 2.50-3.07 (2H, m), 4.10 (2H, q), 4.56 (2H, d), 5.10-5.56 (2H, m), 5.63-6.50 (1H, m), 7.05 (1H, d, J =10 Hz), 7.67 (1H, br), 8.07 (1H, d, J =7 Hz)
EXAMPLE 7 Preparation of Compound No. 5 (Table 2)
Substantially the same operation as in Example 6 was repeated except that 4-chloro-2-fluoro-5-propargyloxyaniline was used as the aniline derivative to obtain the Compound No. 5.
m.p.: 76° C.-77° C.
1 H-NMR (CDCl3, δ ppm) 1.13 (3H, t), 1.00-2.35 (8H, m), 2.50 (1H, t), 2.63-3.20 (2H, m), 4.08 (2H, q), 4.73 (2H, d), 7.10 (1H, d, J =10), 7.76 (1H, br), 8.20 (1H, d, J =7)
EXAMPLE 8 Preparation of Compound No. 6 (Table 2)
Substantially the same operation as in Example 6 was repeated except that 2-chlorocarbonyl-1-cyclohexane carboxylic acid allyl ester was used as the acid halide, and 4-chloro-2-fluoro-5-isopropoxyaniline was used as the aniline derivative to obtain the Compound No. 6.
Refractive Index: nD 25 1.5308
1 H-NMR (CDCl3, δ ppm) 1.26 (6H, d), 1.17-2.60 (8H, m), 2.60-3.20 (2H, m), 4.30-4.76 (1H, m), 4.56 (2H, d), 5.00-5.46 (2H, m), 5.50-6.30 (1H, m), 7.07 (1H, d, J =10), 8.05 (1H, d, J=7)
EXAMPLE 9 Preparation of Compound No. 7 (Table 2)
Substantially the same procedure as in Example 6 was repeated except that 2-chlorocarbonyl-1-cyclohexane carboxylic acid propargyl ester was used as the acid halide and 4-chloro-2-fluoro-5-isopropoxyaniline was used as the aniline derivative to obtain the Compound No. 7.
m.p.: 47° C.-48° C.
1 H-NMR (CDCl3, δ ppm) 1.30 (6H, d), 1.13-2.50 (8H, m), 2.34 (1H, t), 2.60-3.25 (2H, m), 4.17-4.67 (1H, m), 4.67 (2H, d), 7.07 (1H, d, J=10), 7.56 (1H, br), 8.05 (1H, d, J =7)
EXAMPLE 10 Preparation of Compound No. 8 (Table 2)
Substantially the same operation as in Example 6 was repeated except that 2-chlorocarbonyl-1-cyclohexane carboxylic acid allyl ester was used as the acid halide to obtain the Compound No. 8.
Refractive Index: nD 25 1.5361
1 H-NMR (CDCl3, δ ppm) 1.26 (8H, m), 2.56-3.17 (2H, m), 4.53 (4H, d), 4.94-5.46 (4H, m), 5.50-6.43 (2H, m), 7.03 (1H, d, J =10), 7.63 (1H, br), 8.63 (1H, d, J =7)
EXAMPLE 11 Preparation of Compound No. 9 (Table 2)
Substantially the same operation as in Example 6 was repeated except that 2-chlorocarbonyl-1-cyclohexane carboxylic acid allyl ester was used as the acid halide and 4-chloro-2-fluoro-5-propargyloxyaniline was used as the aniline derivative to obtain the Compound No. 9.
m.p.: 94° C.-96° C.
1 H-NMR (CDCl3, δ ppm) 1.34-2.43 (8H, m), 2.50 (H, t), 2.59-3.26 (2H, m), 4.56 (2H, d), 4.73 (2H, d), 4.96-5.53 (2H, m), 5.56-6.26 (1H, m), 7.10 (1H, d, J =10), 7.67 (1H, br), 8.16 (1H, d, J =7)
EXAMPLE 12 Preparation of Compound No. 10 (Table 2)
Substantially the same operation as in Example 6 was repeated except that 2-chlorocarbonyl-1-cyclohexane carboxylic acid propargyl ester was used as the acid halide to obtain the Compound No. 10.
Refractive Index: nD 25 1 5470
1 H-NMR (CDCl3, δ ppm) 1.26-2.59 (8H, m), 2.36 (1H, t), 2.63-3.17 (2H, m), 4.56 (2H, d), 4.67 (2H, d), 5.07-5.67 (2H, m), 7.03 (1H, d, J =10), 7.59 (1H, br), 8.00 (1H, d, J =7)
EXAMPLE 13 Preparation of Compound No. 11 (Table 2)
Substantially the same operation as in Example 6 was repeated except that 2-chlorocarbonyl-1-cyclohexane carboxylic acid propargyl ester was used as the acid halide and 4-chloro-2-fluoro-5-propargyloxyaniline was used as the aniline derivative to obtain the Compound No. 11.
m.p.: 89° C.-90° C.
1 H-NMR (CDCl3, δ ppm) 1.33-2.33 (8H, m), 2.40 (1H, t), 2.56 (1H, t), 2.67-3.33 (2H, m), 4.69 (2H, d), 4.79 (2H, d), 7.48 (1H, d, J =10), 7.67 (1H, br), 8.13 (1H, d, J =7)
EXAMPLE 14 Preparation of Compound No. 12 (Table 2)
Substantially the same operation as in Example 6 was repeated except that 2-chlorocarbonyl-1-cyclohexane carboxylic acid allyl ester was used as the acid halide and 4-chloro-2-fluoro-5-(1-methyl-propynyloxy)aniline was used as the aniline derivative to obtain the Compound No. 12.
m.p.: 91° C.-93° C.
1 H-NMR (CDCl3, δ ppm) 1.20-2.60 (12H, m), 2.61-3.22 (2H, m), 4.46-6.32 (6H, m), 7.10 (1H, d, J =10), 7.68 (1H, br), 8.18 (1H, d, J =7)
EXAMPLE 15 Preparation of Compound No. 13 (Table 2)
Substantially the same operation as in Example 6 was repeated except that 2-chlorocarbonyl-1-cyclohexane carboxylic acid propargyl ester was used as the acid halide and 4-chloro-2-fluoro-5-(1-methyl-propenyloxy)aniline was used as the aniline derivative to obtain the Compound No. 13.
Refractive Index: nD 25 1.5378
1 H-NMR (CDCl3, δ ppm) 1.15-2.55 (12H, m), 2.58-3.20 (2H, m), 4.50-6.32 (6H, m), 7.00 (1H, d, J =10), 7.50 (1H, br), 8.00 (1H, d, J =7)
EXAMPLE 16 Test for Evaluation of Effectiveness in Growth Inhibition by Foliage Treatment
The same procedure as in Example 5 was repeated except that the compounds tested were Compound Nos. 4-13. Further, for comparison, the Comparative Compound A described in Example 4 was also tested. The results are shown in Table 6 below.
                                  TABLE 6                                 
__________________________________________________________________________
              Herbicidal Effectiveness                                    
        Rate  Barnyard-                                                   
                    Pale  Slender          Phytotoxicity                  
Compound No.                                                              
        (a.i. g/10a)                                                      
              grass smartweed                                             
                          amaranth                                        
                               Cocklebur                                  
                                     Velvetleaf                           
                                           Wheat                          
                                               Corn                       
                                                  Soybean                 
__________________________________________________________________________
4       60    0     2     5    2     5     0   -- 0                       
        125   2     2     5    2     5     0   -- 1                       
5       30    0     1     5    0     5     0   -- 0                       
        60    0     1     5    0     5     0   -- 0                       
6       60    0     1     5    1     5     0   -- 0                       
        125   0     4     5    3     5     0   -- 1                       
7       60    0     2     4    2     5     0   0  2                       
        125   0     3     4    5     5     0   0  2                       
8       60    0     4     3    3     5     0   0  0                       
        125   2     5     4    5     5     0   0  0                       
9       30    3     5     5    4     5     0   0  0                       
        60    3     5     5    5     5     0   0  0                       
10      30    0     4     5    3     5     0   0  0                       
        60    1     5     5    3     5     0   0  0                       
11      30    3     --    5    3     5     0   0  0                       
        60    4     --    5    4     5     0   0  0                       
12      30    3     5     5    5     5     0   0  2                       
        60    4     5     5    5     5     0   0  2                       
13      30    3     5     5    5     5     0   0  2                       
        60    4     5     5    5     5     0   0  2                       
Comparative                                                               
        30    0     2     3    3     3     1   0  5                       
Compound A                                                                
        60    1     3     4    3     4     2   0  5                       
__________________________________________________________________________
EXAMPLE 17 Test for Evaluation of Effectiveness in Growth Inhibition by Soil Treatment
The same procedure as in Example 4 was repeated except that the compounds tested were Compound Nos. 4-13. For comparison, the Comparative Compound A described in Example 4 was also tested. The results are shown in Table 7 below.
                                  TABLE 7                                 
__________________________________________________________________________
             Herbicidal Effectives                                        
                                      Annual                              
Compound                                                                  
       Rate  Barnyard-                                                    
                   Small flower       broadleaved                         
                                             Phytoxicity                  
No.    (a.i. g/10a)                                                       
             grass umbrellaplant                                          
                          Bulrush                                         
                               Monochoria                                 
                                      weeds  Rice                         
__________________________________________________________________________
4      15    4     5      2    5      5      0                            
       30    5     5      2    5      5      0                            
5      15    5     5      3    5      5      0                            
       30    5     5      5    5      5      0                            
6      30    4     5      4    5      5      0                            
       60    4     5      4    5      5      0                            
7      15    4     5      3    5      5      0                            
       30    4     5      3    5      5      0                            
8      30    4     5      3    5      5      0                            
       60    4     5      5    5      5      0                            
9      15    5     5      2    5      5      0                            
       30    5     5      4    5      5      0                            
10     30    4     5      3    5      5      0                            
       60    5     5      3    5      5      0                            
11     30    5     5      3    5      5      0                            
       60    5     5      4    5      5      0                            
12     15    5     5      3    5      5      0                            
       30    5     5      4    5      5      0                            
13     15    4     5      2    5      5      0                            
       30    5     5      3    5      5      0                            
Comparative                                                               
       30    3     5      3    5      5      2                            
Compound D                                                                
       60    4     5      4    5      5      3                            
__________________________________________________________________________
EXAMPLE 18 Preparation of N-(4-chloro-2-fluoro-5-isopropoxyphenyl)-2-(2-methoxy ethyloxycarbonyl)cyclohexyl carboxylic amide (Compound No. 14 (Table 3))
In 20 ml of methylene chloride, 0.69 g of 1,2,3,4,5,6-hexahydrophthalic acid 2-methoxyethyl monoester was dissolved. To this solution, 0.24 ml of pyridine and 0.22 ml of thionyl chloride were added and the resulting mixture was stirred at room temperature. One hour later, 0.57 g of 4-chloro-2-fluoro-5-isopropoxyaniline and 0.42 ml of triethylamine were added to the mixture and the mixture was stirred at room temperature for 1.5 hours. After completion of the reaction, 10% hydrochloric acid was added to the reaction mixture to make the same acidic, and the mixture was extracted twice with methylene chloride. The extract was washed with saturated aqueous sodium hydrogen carbonate solution and was dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure and the residue was purified by column chromatography (silica gel, hexane/ethyl acetate =3/1 (v/v)) to obtain 0.59 g of solid.
m.p.: 58° C.-60° C.
______________________________________                                    
Element Analysis                                                          
         C           H      N                                             
______________________________________                                    
Found (%)  57.47         6.42   3.36                                      
Calcd. (%) 57.76         6.54   3.36                                      
______________________________________
NMR (CDCl3, δ ppm) 1.15-2.25 (14H, m), 2.60-3.16 (2H, m), 3.27 (3H, s), 3 30-3.70 (2H, m), 4.15-4.70 (3H, m), 7.05 (1H, d, J =10 Hz), 7.67 (1H, br), 8.16 (d, 1H, J =7 Hz)
EXAMPLE 19 Preparation of Compound No. 15 (Table 3)
Substantially the same procedure as in Example 18 was repeated except that 5-allylthio-4-chloro-2-fluoroaniline was used as the aniline derivative to obtain the Compound No. 15.
Refractive Index: nD 1.5587
______________________________________                                    
Element Analysis                                                          
         C           H      N                                             
______________________________________                                    
Found (%)  56.08         5.7    2.92                                      
Calcd. (%) 55.87         5.86   3.25                                      
______________________________________
NMR (CDCl3, δ ppm) 1.15-2.62 (8H, m), 2.65-3.17 (2H, m), 3.30 (3H, s), 3.40-3.65 (4H, m), 4.15-4.38 (2H, m), 4.95-6.20 (3H, m), 7.09 (1H, d, J =10), 7.67 (1H, br), 8.35 (1H, d, J =8)
EXAMPLE 20 Preparation of Compound No. 16 (Table 3)
Substantially the same procedure as in Example 18 was repeated except that 4-chloro-2-fluoro-5-propargyloxyaniline was used as the aniline derivative to obtain the Compound No. 16.
m.p.: 92° C.-93° C.
______________________________________                                    
Element Analysis                                                          
         C           H      N                                             
______________________________________                                    
Found (%)  57.95         5.71   3.66                                      
Calcd. (%) 58.32         5.62   3.4                                       
______________________________________
NMR (CDCl3, δ ppm) 1.15-2.42 (8H, m), 2.56 (1H, t, J =2), 2.65-3.15 (2H, m), 3.30 (3H, s), 3.35-3.65 (2H, m), 4.06-4.38 (2H, m), 4.72 (2H, d, J =2), 7.12 (1H, d, J =10), 7.76 (1H, br), 8.12 (1H, d, J =7)
EXAMPLE 21 Preparation of Compound No. 17 (Table 3)
Substantially the same procedure as in Example 18 was repeated except that 4-chloro-2-fluoro-5-(1-methyl-propynyloxy)aniline was used as the aniline derivative to obtain the Compound No. 17.
m.p.: 68° C.-70° C.
______________________________________                                    
Element Analysis                                                          
         C           H      N                                             
______________________________________                                    
Found (%)  59.45         5.72   3.5                                       
Calcd. (%) 59.22         5.91   3.28                                      
______________________________________
NMR (CDCl3, δ ppm) 1.15-2.40 (11H, m), 2.50 (1H, d, J =2), 2.60-3.20 (2H, m), 3.25 (3H, s), 3.40-3.65 (2H, m), 4.10-4.35 (2H, m), 4.90 (1H, dq, J =2.6), 7.08 (1H, d, J =10), 7.65 (1H, br), 8.20 (1H, m)
EXAMPLE 22 Preparation of Compound No. 18 (Table 3)
Substantially the same procedure as in Example 18 was repeated except that 4-chloro-2-fluoro-5-(1-methyl-3-butynyloxy)aniline was used as the aniline derivative to obtain the Compound No. 18.
Refractive Index: nD 25 1.5330
______________________________________                                    
Element Analysis                                                          
          C          H      N                                             
______________________________________                                    
Found (%)   60.22        6.07   2.79                                      
Calcd. (%)  60.06        6.18   3.18                                      
______________________________________
NMR (CDCl3, δ ppm) 1.15-3.15 (16H, m), 3.28 (3H, s), 3.32-3.62 (2H, m), 4.00-4.65 (3H, m), 7.02 (1H, d, J =10), 7.60 (1H, br), 8.02 (1H, d, J =7)
EXAMPLE 23 Preparation of Compound No. 19 (Table 3)
Substantially the same procedure as in Example 18 was repeated except that 4-chloro-2-fluoro-5-(4-methoxy-2-butynyloxy)aniline was used as the aniline derivative to obtain the Compound No. 19.
Refractive Index: nD 25 1.5339
______________________________________                                    
Element Analysis                                                          
          C          H      N                                             
______________________________________                                    
Found (%)   57.78        5.81   3.01                                      
Calcd. (%)  57.95        5.96   3.07                                      
______________________________________
NMR (CDCl3, δ ppm) 1.15-2.50 (8H, m), 2.55-3.08 (2H, m), 3.15-3.68 (8H, m), 3.95-4.30 (4H, m), 4.72 (2H, t, J =1), 7.02 (1H, d, J =10), 7.65 (1H, br), 8.12 (1H, d, J =7)
EXAMPLE 24 Preparation of Compound No. 20 (Table 3)
Substantially the same procedure as in Example 18 was repeated except that 4-chloro-2-fluoro-5-propargylthioaniline was used as the aniline derivative to obtain the Compound No. 20.
Refractive Index: nD 25 1.5612
______________________________________                                    
Element Analysis                                                          
          C          H      N                                             
______________________________________                                    
Found (%)   56.16        5.30   2.97                                      
Calcd. (%)  56.13        5.41   3.27                                      
______________________________________
NMR (CDCl3, δ ppm) 1.20-2.60 (9H, m), 2.70-3.25 (2H, m), 3.32 (3H, s), 3.34-3.80 (4H, m), 4.10-4.45 (2H, m), 7.20 (1H, d, J =10), 7.83 (1H, br), 8.48 (1H, d, J =7)
EXAMPLE 25 Preparation of Compound No. 21 (Table 3)
Substantially the same procedure as in Example 18 was repeated except that 2,4-dichloro-5-(1-methyl-propynyloxy)aniline was used as the aniline derivative to obtain the Compound No. 21.
Refractive Index: nD 25 1.5437
______________________________________                                    
Element Analysis                                                          
          C          H      N                                             
______________________________________                                    
Found (%)   56.81        5.67   3.17                                      
Calcd. (%)  57.02        5.69   3.16                                      
______________________________________
NMR (CDCl3, δ ppm) 1.15-2.37 (11H, m), 2.50 (1H, d, J =2), 2.60-3.13 (2H, m), 3.24 (3H, s), 3.30-3.63 (2H, m), 4.05-4.32 (2H, m), 4.90 (1H, dq, J =1, 7), 7.25 (1H, s), 7.85 (1H, br), 8.28 (1H, d, J =2)
EXAMPLE 26 Preparation of Compound No. 22 (Table 3)
Substantially the same procedure as in Example 21 was repeated except that 2-chlorocarbonyl-1-cyclohexane carboxylic acid 2-tetrahydrofuranylmethyl ester was used as the acid halide to obtain the Compound No. 22.
m.p.: 101° C.-102° C.
______________________________________                                    
Element Analysis                                                          
          C          H      N                                             
______________________________________                                    
Found (%)   60.88        6.13   3.22                                      
Calcd. (%)  61.12        6.02   3.09                                      
______________________________________
NMR (CDCl3, δ ppm) 1.15-2.35 (15H, m), 2.50 (1H, d, J =2), 2.57-3.20 (2H, m), 3.50-4.35 (5H, m), 4.85 (1H, dq, J =2,6), 7.12 (1H, d, J =10), 7.73 (1H, br), 8.20 (1H, dd, J =2,
EXAMPLE 27 Preparation of Compound No. 23 (Table 3)
Substantially the same procedure as in Example 18 was repeated except that 4-chloro-2-fluoro-5-(1-cyanoethoxy)aniline was used as the aniline derivative to obtain the Compound No. 23.
m.p.: 79° C.-82° C.
______________________________________                                    
Element Analysis                                                          
          C          H      N                                             
______________________________________                                    
Found (%)   55.93        5.53   6.52                                      
Calcd. (%)  56.27        5.66   6.56                                      
______________________________________
NMR (CDCl3, δ ppm) 1.20-2.50 (11H, m), 2.60-3.10 (2H, m), 3.15-3.70 (5H, m), 4.08-4.38 (2H, m), 4.92 (1H, q, J =7 ), 7.12 (1H, d, J =10), 7.74 (1H, br), 8.24 (1H, d, J =7)
EXAMPLE 28 Preparation of Compound No. 24 (Table 3)
Substantially the same procedure as in Example 18 was repeated except that 4-chloro-2-fluoro-5-[1-(3-methyl-1,2,4-oxadiazol-5-yl) ethoxy)aniline was used as the aniline derivative to obtain the Compound No. 24.
Refractive Index: nD 25 1.5300
______________________________________                                    
Element Analysis                                                          
          C          H      N                                             
______________________________________                                    
Found (%)   54.83        5.59   8.79                                      
Calcd. (%)  54.60        5.62   8.68                                      
______________________________________
NMR (CDCl3, δ ppm) 1.20-2.20 (11H, m), 2.35 (3H, s), 2.65-3.10 (2H, m), 3.25 (3H, s), 3.30-3.60 (2H, m), 4.30-4.40 (2H, m), 5.45 (1H, q, J =7), 7.03 (1H, d, J =120), 7.58 (1H, br), 8.06 (1H, d, J =7)
EXAMPLE 29 Preparation of Compound No. 25
Substantially the same procedure as in Example 18 was repeated except that 4-chloro-2-fluoro-5-[1-(4-methoxybenzenesulfonylamiono carbonyl)ethoxy)aniline was used as the aniline derivative to obtain the Compound No. 25 (viscose substance).
______________________________________                                    
Element Analysis                                                          
          C          H      N                                             
______________________________________                                    
Found (%)   52.55        5.42   4.6                                       
Calcd. (%)  52.72        5.24   4.55                                      
______________________________________
NMR (CDCl3, δ ppm) 1.05-2.50 (11H, m), 2.58-3.12 (2H, m), 3.28 (3H, s), 3.40-3.68 (2H, m), 3.82 (3H, s), 4.10-4.40 (2H, m), 4.67 (1H, q, J =7), 6.80-7.20 (4H, m), 7.60-8.15 (4H, m)
EXAMPLE 30 Test for Evaluation of Effectiveness in Growth Inhibition by Soil Treatment
The same procedure as in Example 4 was repeated except that the compounds tested were Compound Nos. 14-25. For comparison, the Comparative Compound A described in Example 4 was also tested. The results are shown in Table 8 below.
                                  TABLE 8                                 
__________________________________________________________________________
                                    Annual                                
Compound                                                                  
       Rate     Barnyard-                                                 
                      Small flower  broadleaved                           
No.    (a.i. g/10a)                                                       
             Rice                                                         
                grass umbrellaplant                                       
                             Monochoria                                   
                                    weeds                                 
__________________________________________________________________________
14     60    0  5     5      5      5                                     
       30    0  4     5      5      5                                     
15     60    0  5     5      5      5                                     
       30    1  5     5      5      5                                     
16     60    0  5     5      5      5                                     
       30    0  4     5      5      5                                     
17     60    0  5     5      5      5                                     
       30    0  4     5      5      5                                     
18     60    0  5     5      5      5                                     
       30    0  4     5      5      5                                     
19     60    0  5     5      5      5                                     
       30    0  4     5      5      5                                     
20     60    0  5     5      5      5                                     
       30    0  4     5      5      5                                     
21     60    0  5     5      5      5                                     
       30    0  4     5      5      5                                     
22     60    0  5     5      5      5                                     
       30    0  4     5      5      5                                     
23     60    0  5     5      5      5                                     
       30    0  4     5      5      5                                     
24     60    0  5     5      5      5                                     
       30    0  4     5      5      5                                     
25     60    0  5     5      5      5                                     
       30    0  4     5      5      5                                     
Compara-                                                                  
       60    3  4     5      5      5                                     
tive   30    2  3     5      4      5                                     
Compound A                                                                
__________________________________________________________________________
EXAMPLE 31 Test for Evaluation of Effectiveness in Growth Inhibition by Foliage Treatment
The same procedure as in Example 5 was repeated except that the compounds tested were Compound Nos. 14-25. Further, for comparison, the Comparative Compound A described in Example 4 was also tested. The results are shown in Table 9 below.
                                  TABLE 9                                 
__________________________________________________________________________
                    Herbicidal Effectiveness                              
        Rate  Barnyard-                                                   
                    Pale  Slender          Phytotoxicity                  
Compound No.                                                              
        (a.i. g/10a)                                                      
              grass smartweed                                             
                          amaranth                                        
                               Cocklebur                                  
                                     Velvetleaf                           
                                           Wheat                          
                                               Corn                       
                                                  Soybean                 
__________________________________________________________________________
14      60    5     5     5    5     5     0   0  2                       
        30    4     5     5    4.5   5     0   0  2                       
15      60    5     5     5    5     5     0   0  2                       
        30    5     5     5    5     5     0   0  1                       
16      60    5     5     5    5     5     0   0  2                       
        30    5     5     5    5     5     0   0  2                       
17      60    5     5     5    5     5     1   0  2                       
        30    4     5     5    5     5     1   0  2                       
18      60    0     5     5    5     5     0   0  1                       
        30    0     3     5    5     5     0   0  1                       
19      60    4     4     5    5     5     0   0  1                       
        30    3     2     4    5     5     0   0  1                       
20      60    5     4     5    5     5     0   0  2                       
        30    5     4     5    5     5     0   0  1                       
21      60    4     5     5    5     5     0   0  2                       
        30    4     5     5    5     5     0   0  2                       
22      60    3     5     5    5     5     1   0  2                       
        30    3     5     4    5     5     0   0  1                       
23      60    4     5     5    5     5     0   0  2                       
        30    4     5     5    5     5     0   1  2                       
24      60    4     5     5    4     5     0   0  0                       
        30    4     4     5    3     5     0   0  0                       
25      60    0     0     5    4     5     0   0  0                       
        30    0     0     5    3     5     0   0  0                       
Comparative                                                               
        60    1     3     3    3     4     2   0  5                       
Compound A                                                                
        30    0     2     2    3     3     1   0  5                       
__________________________________________________________________________

Claims (8)

We claim:
1. A hexahydrophthalic anilide derivative of the formula [I]: ##STR13## wherein R1 represents non-substituted or substituted phenyl, R2 represents hydrogen or C1 -C4 alkyl, R3 represents C1 -C4 alkyl or C1 -C4 alkenyl.
2. The hexahydrophthalic anilide derivative of claim 1, wherein R1 represents phenyl.
3. A hexahydrophthalic anilide derivative of the formula [II]: ##STR14## wherein R4 and R5, the same or different, represent C1 -C4 alkyl, C1 -C4 alkenyl or C1 -C4 alkynyl, provided R4 and R5 are not C1 -C4 alkyl simultaneously.
4. A hexahydrophthalic anilide derivative of the formula: ##STR15## wherein X1 and X2, the same or different, represent halogen Y, represents oxygen or sulfur, R6 represents C1 -C6 straight alkyl group which is substituted with a C1 -C3 alkoxy group, tetrahydrofurfuryl or 2-perhydropyranylmethyl, R7 represents hydrogen or methyl, R8 represents cyano, C1 -C3 alkyl, C2 or C3 alkenyl, C2 -C4 alkynyl, C3 -C6 alkynyl which is substituted with methoxy, CONHR9, wherein R9 represents aromatic sulfonyl, or an azole heterocyclic ring.
5. The hexahydrophthalic anilide derivative of claim 4, wherein X1 and X2, the same or different, represent fluorine or chlorine.
6. The hexahydrophthalic anilide derivative of claim 5, wherein R6 represents methoxyethyl or tetrahydrofurfuryl.
7. The hexahydrophthalic anilide derivative of claim 5, wherein R8 represents 1,2,4-oxadiazolyl or which 3-position is substituted with C1 -C3 alkyl.
8. The hexahydrophthalic anilide derivative of claim 5, wherein R9 represents anisyl sulfonyl.
US07/292,077 1987-12-31 1988-12-30 Hexahydrophthalic anilide derivatives Expired - Fee Related US5068365A (en)

Applications Claiming Priority (8)

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JP33645287A JPH01175961A (en) 1987-12-31 1987-12-31 Hexahydrophthalanilide acid derivative, production thereof and herbicide comprising said derivative and active ingredient
JP62-336452 1987-12-31
JP62-222256 1988-09-07
JP22225688A JPH0272145A (en) 1988-09-07 1988-09-07 Hexahydrophthalic acid anilide derivative, production thereof and herbicide containing said derivative as active ingredient
JP22546288A JPH0273047A (en) 1988-09-08 1988-09-08 Hexahydrophthalic acid anilide derivative, preparation thereof and herbicide containing said derivative as active ingredient
JP63-225462 1988-09-08
JP63234259A JPH0283359A (en) 1988-09-19 1988-09-19 Hexahydrophthalic acid anilide derivative, its production and herbicide containing the same derivative as active component
JP63-234259 1988-09-19

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US5481022A (en) * 1992-12-02 1996-01-02 Central Glass Company, Ltd. N-aryloxyacyl-n-phenyltetrahydrophthalamic acid derivatives, methods of producing same, and herbicides containing same as effective components
US5801122A (en) * 1994-01-19 1998-09-01 Central Glass Co., Ltd. N-phenyltetrahydrophthalamic acid derivatives, methods of producing same, and herbicides containing same as effective components
WO2023077057A1 (en) * 2021-10-28 2023-05-04 H. Lee Moffitt Cancer Center And Research Institute, Inc. Small-molecular inhibitors for the beta-catenin/ b-cell lymphoma 9 protein-protein interaction

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AU638349B2 (en) * 1990-07-17 1993-06-24 Kaken Pharmaceutical Co., Ltd. Heterocycle-substituted benzene derivative, production thereof, and herbicide containing the same as active ingredient

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US5481022A (en) * 1992-12-02 1996-01-02 Central Glass Company, Ltd. N-aryloxyacyl-n-phenyltetrahydrophthalamic acid derivatives, methods of producing same, and herbicides containing same as effective components
US5801122A (en) * 1994-01-19 1998-09-01 Central Glass Co., Ltd. N-phenyltetrahydrophthalamic acid derivatives, methods of producing same, and herbicides containing same as effective components
US6337417B1 (en) * 1994-01-19 2002-01-08 Central Glass Co., Ltd. N-phenyltetrahydrophthalamic acid derivatives, methods of producing same, and herbicides containing same as effective components
WO2023077057A1 (en) * 2021-10-28 2023-05-04 H. Lee Moffitt Cancer Center And Research Institute, Inc. Small-molecular inhibitors for the beta-catenin/ b-cell lymphoma 9 protein-protein interaction

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